Process of alkylating hydrocarbons



Patented June 16, 194 2 v p I UNITED ST TES PATENT, OFFICE v l raocsss or a lggggrma m nim Heinz Heinemann, Pittsburgh, Pa., assignor to the firm Danciger Oil & Refineries, Ina, Tulsa, Okla.

No Drawing. Application July 10, 1941,

I Serial No. 401,788

18 Claims. (Cl. 196-10) This invention relates to a catalytic process of fying the aqueous solution of a salt of an antialkylating hydrocarbons and it has particular monic acid, such as a saltof H3Sb04, Hisbio'l, or relation to a process oi. alkylating iso-parafilns HSbOa. V with olefins. For instance, 1 partby weight of antimony The known processes of alkylatingiso-paraflins .pentachloride is added gradually to about an with an olefin are catalytic and noncatalytic in equal weight of water. This causes the formanature. The noncatalytic processesrequire very tion of a white precipitate whichprobably conhigh temperatures and pressures. In the catasists of hydrates of. antimony pentoxide. This lytic processes the catalysts used in the main, product, however, may contain, besides the hyare sulfuric acid and aluminum chloride, with drates of antimony pentoxide, hydrolysis prodor without activators. Phosphoric acid preparanets of antimony trichloride. The presence of tions have appeared in the literature recently for compounds of trivalent antimony may be surthe purpose of alkylation. 1 mised because of the detection by odor of chlo- It has been found that the process of alkylatrine evolved during the reaction between the waing iso-paraflins with olefins, such as ethylene, ter and antimony pentachloride. The white prepropylene, butylene, and their homologues, can cipitate is brought upon a filter and washed with be carried out with particular advantage by causwater until the filtrate is substantially free from ing the reaction components to react at an elechlorine ion, and added under agitation to a 10% vated temperature and under superatmospheric solution of zinc chloride in water. The antimony pressure in the presence of a catalyst which con- 0 precipitate obtained from 2 to 5 parts by weight tains as active ingredient a metal halide selectof, antimony pentachloride, may be added to ed from the group consisting of the halides of about 1000 parts by weight of a 10%aqueous s0- zinc, aluminum, iron, and tin, particularly zinc 'lution of zinc chloride, for xample.

chloride, aluminum chloride, ferric chloride, Solid carriers, such as silica-gel, diatomaceous stannic chloride, and, as an activator or promot- 25. earth, kieselguhr, bentonite, activated carbon, er, an oxygen containing compound of antimony fullers earth or alumina, may also be employed selected from the group consisting of antimony -in the preparation of the catalystused in the compounds obtained by 'hydrolytic decomposiprocess of the present invention. For example, tion in aqueous solution, of a water-soluble comgrams of zinc chloride are dissolvedin 20. cc. pound of antimony, oxides and oxide hydrates :w of water and homogenized with a suspension of of antimony, oxy-acids of antimony, and anti-' 1 gram of antimony. compound suspended in 10 mony compounds obtained by acidifying an aquecc. of water, said antimony compound being obous solution of an antimonic salt. The metal tained as describedaboveby the action of water halide antimony compound mixture of the type on antimony penta chloride. The mixture of zinc described may consist ofone or more metal halchloride solution and antimony compound is addides together with one or more antimony comed in portions to 185 grams of activated alumina, pounds referred to. In the catalytic composiand agitated rapidly until the mixture i dry. tion used for carrying out the process of this inv The catalytic compositions of the. above dev'ention, the metal halide may be present wholly scribed type are substantially non-corrosive, and or partly dissolved in water. A saturated metal in they can be used for a relatively long time withhalide solution which contains an undissolved out substantial reduction of their efliciency. A excess of the metal halide may, for example, be further advantage affordedv by the use of the d,- I catalyst and process described is that it will The above mentioned antimony compounds alkylate iso-parafllns with any :olefln including may-be prepared in any suitable manner. Ipreethylene. This is not the case with catalysts fer, for instance, the treatment with water of" heretofore known.

antimony pentachloride, antimony pentafluoride, The invention may be illustrated by the followantimony pentachloride hydrate or hydrochloric ing examples:

acid solution of antimony pentachloride, or the Example I.A mixture consisting of 66%% by decomposition of an aqueous solution of a salt volume of, ethylene and 33' /3% by volume of 15 of an antimonic acid with anacid. A single com- 1 butane, is heated in a reaction chamber at 400 pound of antimony or a mixture of several com- F. under a gauge pressure of 400 lbs. per square pounds may be used. Suitable antimony cominch for a period of one hour, in the presence pounds are, for example, Sb2O5.H2O, Sb2O5.2H2O, of a catalyst consisting of 900 parts or water, 96 Sb2O5.3HzO, or the precipitates obtained by acidi- ,parts of zinc chloride and the product of hydrolysis oi 4 parts of antimony pentachloride. The reaction product separated irom the catalyst, contained, besides the excess ethylene and the unused iso-butane, some liquid, amounting to a calculated yield oi 70% by weight, based upon the iso-butane charge to th reaction. The catalyst, after separation irom the reaction mixture, is available for the reaction between iurther quantities oi ethylene and iso-butane.

The product irom the alkylation of lac-butane with ethylene, under the conditions given, had an octane number oi 91, and contained a considerable proportion oi neohexane.

The process may also be carried out in continuous operation, the details oi such continuous process and the necessary modifications oi the above described procedure being obvious to those skilled in the art.

The ratio oi the antimony compound to the metal halide is of great importance to the conversion, as is illustrated in the following table, showing in the first two columns the weight in grams oi zinc chloride, and of the antimony penta-chloride used for the preparation oi the activator, that was added to 900 cc. oi water, to term the catalyst, and in the last column the percent conversion to alkylateibased upon the isobutane charge to the reaction vessel) after heating the reaction mixture at 400 F. under a pressure of 400 lbs. per'square inch for a period of an hour:

Wdght znon Weight such Per cent as 5 s2 Example II.A mixture of 30 parts by weight oi zinc chloride, 30 parts oi water, and one part oi antimony compound were well mixed with 185 D rts oi activated alumina. .A mixture oi 1.7 parts by volume oi iso-butane and 1.0 parts by volume oi butylene, said butylene being prepared by the dehydration oi normal butyl alcohol over alumina at 850 F., was maintained at a temperature of 400 F. and a pressureoi 445 lbs. per square inch, in the presence oi the above catalyst ior a period oi 65 minutes, this period oi time being taken to attain the reaction temperature. The yield 01' alkylate amounted to 41.5% oi the theoretical and the alkylate had an octane blending value oi 90. Inthe presence oi 3 cc. oi'tetraethyl lead per gallon oi blend, its octane blending value was 92, showing that it had both a high octane number and a high lead susceptibility.

between 200 and 1000 pounds or more per square inch. I preier the use oi temperatures between 300' and 500 F. and the use oi a pressure of 300 to 450 lbs. per square inch.

The reaction between iso-paraiiin's and olefins according to this invention may be carried out in the presence oi impurities or other compounds which do not adversely aiiect the alkylation. For

example, the iso-butane present in hydrocarbon gas mixtures maybe utilized in the process oi this invention, or iso-paraiiins and olefins, which are obtained in cracking may be subjected to reaction conditions inthe presence oi the catalyst. The iso-parafilns and oleiins may also be used i pure condition. Y

The above examples are given merely ior purposes oi illustration. Variousmodifications are possible and will be apparent. Other modifications and changes may bemade by those skilled in the art without departing from the nature and scope oi the invention as defined in the appended claims. h

Reference is made to my co-pending application Serial No. 370,738, filed December 19, 1940.

I claim:

l. A process oi alkylating iso-paramns with olefins, said process comprising reacting an isoparamn with an olefin at a temperature oi 300 to 500' I". and under a pressure oi 300 to 450 lbs. per square inch, in the presence oi a catalytic composition containing a metal halide selected irom the group consisting oi zinc halides, aluminum halides, ierric halides, and stannic halides, in mixture with an oxygen containing compound oi antimony selected irom the group consisting oi antimony compounds obtained by hydrolytic decomposition in aqueous solution, oi a watersolubie compound oi antimony, oxides and oxide hydrates oi antimony, oxy-acids oi antimony, and antimony compounds obtained by acidifying an aqueous solution oi a salt oi an antimonic acid.

2. A process oi alkylating iso-parailins with olefins, said process comprising reacting an iso- Alkylation of iso-paramns with oleflns can be eflected at temperatures between 300 and 1000 F., depending on the pressure used, which varies 7s paraiiin withan olefin at a temperature oi 300 to 500' F. and under a pressure oi 300 to 450 lbs. per square inch, in the presence of a catalytic composition containing a metal halide selected irom the groupconsisting of zinc halides, aluminum halides, ierric halides, and stannic halides, said metal halide being at least partly dissolved in water, in mixture with an oxygen containing a compound of antimony selected irom the group consisting of antimony compounds obtained by hydrolytic decomposition in aqueous solution, oi a water-soluble compound oi antimony, oxides and oxide hydrates oi antimony, oxy-acids oi antimony, and antimony compounds obtained by acidifying an aqueous solution oi a salt oi an antimonic acid.

, 3. A processoi alkylating iso-paraiilns with olefins, said process comprising reacting an isoparaiiln with an olefin at a temperature of 300 to 500 F., and under a pressure 01' 300 to 450 lbs. per square inch, in the presence of a catalytic composition containing a solid-carrier substance, and a metal halideselected irom the group consisting oi zinc halides, aluminum halides, ierric halidesand stannic halides, in mixture with an o y en containing compound of antimony selected from the group consisting oi antimony compounds obtained by hydrolytic decomposition in aqueous solution, oi a water-soluble compound oi antimony, oxides and oxide hydrates oi antimony, oxy-a'cids oi antimony, and antimony compounds obtained by acidifying an aqueous solution of a salt of an antimonic acid.

4. A process of alkylating iso-parafllns with oleflns, said process comprising reacting an iso-, paraiiln with an olefin, at a temperature of 300 to 500 F. and under a pressure of 300 to 450 lbs. per square inch, in the presence of a catalytic composition containing zinc chloride and a precipitate obtained by the action of water on about an equal amount of antimony pentachloride.

5. A process of alkylating iso-paraflins with olefins, said process comprising reacting an isoparafiin with an olefin at a temperature of 300 to 500 F. and under a pressure of 300 to 450 lbs.

per square inch, in the presence or a catalytic composition'containing zinc chloride, which is at least partially dissolved in water and a precipitate obtained by the action of water on about an equal amount of antimony pentachloride.

6. A process-of alkylating iso-paraillns with olefins, said process comprising reacting an isoparaflin with an olefin at a temperature of 300" to 500 F., and under a pressure of 300 to 450 lbs. per square inch,,in the presence of a catalytic composition containing a solid carrier substance, zinc chloride, and a precipitate obtained by the action of water on aboutan equal amount of antimony pentachloride.

7. A process of alkylating iso-butane with ethylene, said process comprising reacting said isobutane with ethylene, at a temperature of about 400 F. and under a pressure of 400 to 450 lbs. per square inch, in the presence of a catalytic composition containing a metal halide selected from the group consisting of zinc halides, aluminum halides, ferric halides and stannic halides, in mixture with an oxygen containing compound of antimony selected from the groupconsistingof antimony compounds obtained by hydrolytic decomposition in aqueous solution, of a water-soluble compound of antimony,oxides and oxide hydrates of antimony, mony, and antimony compounds obtained by acidifying an aqueous solution of a salt of an antimonic acid,

8. A process of alkylating iso-butane withethylene, said process comprising reacting said isobutane'with ethylene at a temperature of about 400 F. and under a pressure of 400 to 450 lbs. per

square inch, in the presence of a catalytic com-. position containing zinc chloride and an oxygen containing compound of antimony selected from the group consisting of antimony compounds obtained by hydrolytic decomposition in aqueous solution, of a water-soluble compound of antimony, oxides and oxide hydrates of antimony, oxy-acids of antimony, and antimony compounds obtained by acidifying an aqueous solution'of a salt of an antimonic acid.

9. A process of alkylating iso-butane with ethylene, said process comprising reacting said isobutane with ethylene at a temperature of about 400 F., and under a pressure of 400 to 450 lbs. per square inch, in the presence of a catalytic composition consisting of 96 parts b. w. of zinc chloride dissolved in 900 parts b. w. of water and the product of hydrolysis of 2 to 5 parts b, w. of

lected from the group consisting of zinc halides, aluminum halides, ferric halides and stannic ,ha-" lides, in mixture with an oxygen containing compound of antimony selected from the group consisting of antimony compounds obtained by hydrolytic decomposition in aqueous solution, of a water-soluble compound of antimony, oxides and oxide hydrates of antimony, oxy-acids of antimony, and antimony compounds obtained by acidifying an aqueous solution of a salt of an antimonic acid. 11. A process of alkylating iso-butane with butylene, said process comprising reacting said iso-butane with butylene at a temperature of about 400 F. and under a pressure of 400 to 450 lbs. per square inch, in the presence of 'a catalytic composition containing zinc chloride and an oxygen containing compound of antimony selected from the group consisting of antimony compounds obtained by hydrolytic decomposition in aqueous solution, of a water-soluble compound of antimony, oxides and oxide hydrates of antimony, oxy-acids of antimony, and antimony compounds obtained by acidifying an aqueous solution of a salt of an antimonic acid.

12. A process of alkylating iso-butane with butylene, said process, comprising reacting said iso-butane with butylene at a temperature. of about 400 F. and under a pressure of 400 to 450 lbs. per square inch, in the presence of a catalytic composition consisting of 96 parts b. w. of zinc chloride dissolvedin 900 parts b. w. of water and the product of hydrolysis of 2 to 5 parts b. w.

I of water on about an equal amount of antimony oxy-acids of antiwater on about an equal amount of antimony pentachloride.

10. A process of alkylating iso-butane with pentachloride.

13. A process ofalkylating iso-butane with ethylene, said process comprising reacting said iso-butane with ethylene at a temperature of about 400 F. and under a pressure of 400 to 450' lbs.per square inch, in the presence of a catalytic composition consisting of a mixture of about 30 parts by weight of zinc chloride, about 30 parts b. w. of water, 1 to 2 parts of antimony compoundsobtained by hydrolytic action of water on about an equal amount of antimony pentachloride, and 185 parts by weight of activated alumina.

14. A process of alkylating iso-butane with butylene, said process comprising reacting said iso-butane with butylene at a temperature of about 400 F. and under a pressure of 400 to 450 lbs. per square inch, in the presence of a catalytic composition consisting of a mixture of about 30 parts b. w. of zinc chloride, about-30 parts b. w. of water, 1 to 2 parts of antimony compounds obtained by hydrolytic action of wateron about an equal amount of antimony pentachloride, and 185 parts by weight of activated-alumina.

15. In a process of alkylatingiso paraflins with oleflns, the step of bringing the reaction mixture of an iso-paraflin and an olefin into contact with a catalyst containing a metal halide, selected from the group consisting of zinc halides, aluminum halides, ferric halides and stannic halides, in mixture with an oxygen containing compound of antimony selected from the group consisting of antimony compounds obtained by hydrolytic decomposition in aqueous solution, of a water-soluble I compound of antimony, oxides and oxide hydrates of antimony, oxy-acids of antimony, and

antimony compounds obtained by acidifying an aqueous'solution of a salt of an antimonic acid. 16. In a process of alkylating iso-paraiiins with I oleflns, the stepof bringing the reaction mixture lytic composition containing a metal halide seof an iso-parafiinand an olefin into contact with a catalyst containing zinc chloride and the product of hydrolysis of water on about an equal amount of antimony pentachloride.

17. In a process of alkylating iso-parafilns with olefins, the step of bringing a mixture of an isoparafiin with an olefin and other hydrocarbons into contact with a catalyst containing a metal halide selected from the group consisting of zinc halides, aluminum halides, ferric halides and stannic halides in mixture with an oxygen containing compound of antimony selected from the group consisting of antimony compounds obtained by hydrolytic decomposition in aqueous solution, of a water-soluble compound of antimony,' oxides andloxide hydrates oi antimony, oxy-acids oi antimony, and antimony compounds obtained by acidifying an aqueous solution of a salt or an antlmonic acid.

a 18. In a process of alkylatinz iso-parafllns with olefins, the step of brin'a nl a mixture of an isoparaflln with an olefin and other hydrocarbons into contact with a catalyst containing zinc chloride and the product of hydrolysis of water on about an equal amount oi antimony pentachloride.

HEINZ HEINEMANN. 

